Production of water-soluble azo dyestuffs



Patented Nov. 16, 1937 UNITED STATES PATENT OFFICE V l 2,099,525 K orWATER-SOLUBLE AZO DYESTUFFS Hans Krzikalla, Heinrich Dehnert, andDieter.Vossen, Ludwigshafen-on-the-Rhine, Ger-' many, assignors to GeneralAniline-Works, Inc., New York, N. Y., a corporation of Delaware'rRoDUoTIoN No Drawing. Application February 4, 1936, Se-

rial Nor 62,376.. .In Germany February 19, 1935" a 14 Claims; (01.260-96).

The present invention relates to water-soluble azo dyestufis and aprocess of making them.

We have found that valuable water-soluble azo dyestuifs are obtained bycoupling aromatic (obtainable by reactingN-butyl-N-chlorethylaminobenzene with pyridine). The resulting dyestuifis thereby precipitated andafter filtration by suction it is Washed withcommon salt amines of the general formula: solution until neutral." Itdyes cotton, viscose "5 artificial silk ormixed fabrics, leather andpaper brilliant red shades. V Similar dyestufis are obtained by couplingthe compound obtainable from pyridine and N-butylN-chlorethylaminobenzene with the following di- 10 (in which R is anaromatic radicle capable of 3,50 compounds; coupling, X is an alkyl,aryl, aralkylor cycloalkyl group and Y is .an ankyl radicle to which V[Shade Q 1 is attached indirect combination with an alrk kyl carbon atoma quaternary nitrogen atom, m Orange 15 such as the nitrogen atom of theresidue 'l'ammo'zlfidlchlorA'"mtroben" of a quaternary ammonium base oraquara ternary ammonium salt, or in which ,X is the m Orange same as Y)with diazotized aromatic amines. m Yellow Amines of the above mentionedgeneral. for- V mula are obtainable for example from aromatic d 20compounds containing .a chloralkyl group at- 'i dlmethoxydl' tached to atertiary nitrogen atom by reaction Pale brown with pyridine, quinoline,trimethylamine, trieth- Y 'F' S111- anolamine or the like and usuallyconstitute well phqmc a Yellow crystallizing, readily water-soluble andWeakly -a fibasic substances. The dyestuffs obtainable therebenzene Redfrom eoupling diazotjzed aromatic 1amino-2,3,5,6-tetrachlorbenzene Paleyello amines, 285 .for example aniline, phenylene dia-. i A- i e Redmines, benzidine, naphthylamines or their homo- A- loguesyorderivatives'are suitable for dyeing a Z6119 Bordeaux red great variety of materials.Dyestuffs of .thiskind which contain a 'diazotizable amino group, may 7Example 2 be converted into disazo dyestuffs by diazotizing V andcoupling with coupling components, 138 parts of-1-am1no-4-n1trobenzeneare di- The follo ing examples will furthe iuustmte, azotizedin theusual manner and coupled-withan how the said invention may be carriedout in aqueous solution of 1 of h compound 1 practice but the inventionis not restricted to these examples. The parts are by weight.

' o1 Ezvample 1 r 7 40 CHr-OHr-N l'38 parts of lamino l nitro-benz'eneare diazotized in the usual manner and coupled with V an aqueoussolution o'f 307 parts of the reaction V r 1 prbdubtof pyridinewithN-normal-butyl-omega- CH3 3 chlorethylben'zene C H (obtainable fromtrimethylamine and l-methyl- 4 o, 3(N-butyl-N-omegachlorethyl)-aminobenzene) N 7} i j a to which have beenadded 272 parts of crystal- \CHPO'HPBPCI lized sodium acetate. Theresulting dyestuff I r. may be directly filtered 011 by suction and dyesa; great variety of materials red "shades fast to; light. V Similardyestuffs are-obtained .from the compound of the above formula bycoupling with the following compounds:

Shade of color 1-amino-2,4,6-trichlorbenzene Yellow1-amino-23,55tetrachlorbenzene Pale yellow 1-amino-2,4-dinitrobenzeneRed-violet 1-amino-2-chlor-l-nitrobenzene Dark red1-amino-2,6-dichlor-4-nitrobenzene Brown-red 1amino-2,4,5trichlorbenzeneOrange l-amino-G-bromo-2.4-dinitrobenzene. Violet Example 3 138 parts ofl-amino-l-nitrobenzene are diazotized in the usual manner and coupledwith an aqueous solution of 330 parts of the compound CzHlOH (obtainablefrom pyridine and N-hydroxyethyl- N (beta hydroxy gammachlorpropyl)-aminobenzene) to which have been added 212 parts of calcined sodiumcarbonate. The resulting dyestufi dyes a great variety of materialspowerful red shades.

Example 4 196 parts of l-amino-2,4,6-trichlorbenzene are diazotized andcoupled with 300 parts of the compound (derived from trimethylamine andN-omegachlorethyldiphenylamine) in 10,000 parts of water. The solutionis then almost neutralized with sodium acetate and the precipitateddyestuff filtered off by suction. It dyes viscose artificial silk andleather beautiful green-yellow shades. Especially deep shades areobtained (as also with the dyestuffs already specified) in leather whichhas been prepared with synthetic tanning agents containing sulphonicgroups.

Similar valuable dyestuifs are obtained with the following diazotizedamines:

Shade of color 1-amlno-2,4-dinitrobenzene Red 1-amino-4-nitrobenzenePale red l-amino-2-ch.lor-4-nitrobenzene Brown-red1-amino-2,6-dichlor-4-nitrobenzene- Brown l-amino-2,4,5-trichlorbenzeneYellow Example 5 138 parts of l-aminol-mtrobenzene are diazotized andcoupled with an aqueous solution of 250 parts of the reaction productderived from trimethylamine or triethanolamine and N-ethyl-N-omega-chlorethylaminobenzene, viz:-

to which sodium acetate has been added. The

resulting dyestufi dyes a great variety of mate rials brilliantorange-red shades. (By employing the reaction product derived fromtriethanolamine and N-hydroxyethyl-N-omega-chlorethylaminobenzene, asimilar dyestuff is obtained.)

In a. similar manner dyestuffs having good properties as regardsfastness are obtained by coupling the compound prepared fromtrimethylamine or triethanolamine andN-ethyl-N-omegachlorethyl-aminobenzene with the following diazotizedamines Shades of color l-amino -2, l,6-trichlorbenzene Yellow 1-amino-2,4,5 -trichlorbenzene Yellow l-amino-2,3,5,6-tetrach1orbenzeneGreen-yellow l-amino-2,6-dichlor-4-nitrobenzene Red-brown1-amino-2,4-dir1itrobenzene Red l-amino-6-bromo-2,4-dinitrobenzeneBlue-red 4-amino-azo-toluene Red l-amino-naphthalene Yellow 4-nitro-4-amino-azo-benzene Red Dyestuffs of this kind are also soluble innitrocellulose lacquers.

Example 6 By coupling l-aminol-nitrobenzene with the reaction productderived from two molecular proportions of trimethylamine with 1molecular proportion of N-di-(chlorethyD-aniline and having the formula:

C Ha- C Hz-N 0 Ha III:

The diazo compound of 262 parts of l-amino- ZA-dinitro-6-brombenzene iscoupled with the reaction product derived from trimethylamine andN-ethyl-N-omega-chlorethyl-l-aminonaphthalene and having the formula:

The dyestuff thus formed dyes leather bluish violet shades. 1

. A dyestufi having similar properties is obtained by coupling the samediazo compound with the reaction product derived from trimethylamine andN-butyl-N-omega-chlorethyl 1 amino -2- methoXy-5-methylbenzene.

Example 8 The diazo compound of 231 parts of 2, 3, 5, 6-tetrachlor-l-aminobenzene is coupled with the solution in 12000 parts ofwater of the reaction product of dimethyl-stearylamine and N-ethyl-Nechlorethylaminobenzene. .The solution is then neutralized withisodiumacetate and the 'dyestufi precipitated is filtered. oifi by suction. Itdyes chrome-tanned leather- :;which has been treated with synthetictanning-agents" containing sulphonic groups yellow brown shades.

Example 9 thetic tanning agent's containing sulphonic acid groups,strong brown shades, Y

Example 10 231parts of 2,3,5,6-tetrach1or-l-aminobenzene are diazotizedand coupled with 300.5 parts of the reaction product derivedfromtrimethylamine and Nbutyl-N-(beta-hydroxy-gamma-chlorpropyD-aminobenZene. The dyestuffobtained dyes leather which has been prepared with synthetic tanningagents containing sulphonic'acid groups deep yellow shades. I I 4Similar valuable dyestuffs are obtained when employing instead of2,3,5,6-tetrachlor-l-aminobenzene the following amines as diazocomponents:

Shade of color l-amino-2,6-dichlor-4-nitrobenzene Red brown1-arnino-2,4,5-trichlorbenzene Orange l-amino-2,4,6-trichlorbenzene-:Yellow l-amino-l-nitrobenzene 'Red Dyestuffs of this kind are alsosoluble in nitrocellulose lacquersand organic solvents.

'When employing the reaction product derived from trimethylamine and;N-ethyl-N- (beta-hydroxy gamma -chlorpropy1) aminobenzene as couplingcomponent similar dyestuffs are ob-. tained.

Example 11 The diazo solution of 231 parts of2,3,5,6-tetrachlor-l-aminobenzene is coupled with 296.5 parts of thereaction product derived from trimethylamine andN-cyclohexyl-N-omega-chlorethylaminobenzene. The dyestuff thus obtainedyields brilliant yellow shades on different materials.

Example '12 153 parts of l-nitro-1,3-diaminobenzene are monodiazotizedand coupled with 396 parts of the reaction product derived from 2molecular proportions of trimethylamine and 1 molecular proportion ofN-di-(beta-hydroxy-gannna-chlorpropyl) -aminobenzene of the formula 7/CH3 CHPCHOH-CH2N"CH3 After having finished the first coupling processthe resulting monoazo dyestuff is diazotized for ai'second timeand'coup'led with ll2zparts oftdihydro-resorcin. The disazo' dyestuff'obtained is readily soluble in water and dyes leather which has beenpreparedwith synthetic-tanning agents containing sulphonic acid groupsvery fast brown shades. I

What we claim is:

1. A process for the production of water-soluble azo dyestuffs whichconsists in coupling aromatic amines of the general formula wherein R isan aromatic radicle capable of being coupled, and at least one X standsfor analkyl radicle to'which' is attached in direct combination with analkyl carbon atom a quaternary nitrogen atom; the other X being a memberof the group consisting of alkyl, cycloalkyl, aralkyl and aryl, withdiazotized aromatic amines.

2. A process for the production of water-soluble azo dyestufis whichconsists in coupling aromat-ic'amines of the general formula wherein Ris an aromatic radicle capable of being coupled and X stands for amember of the group consisting of alkyl, cycloalkyl, aralkyl and aryl,with diazotized aromatic amines.

4. A process for the production of water-soluble azo dyestufis whichconsists in coupling aromaticamines of the general formula wherein R isan aromatic radiclecapable of being coupled and X stands for alkyl, withdiazotized aromatic amines.

5.-A process for the production of water-soluble azo dyestuffs whichconsists in coupling aromatic amines of the general formula wherein R isan aromaticradicle capable of being coupled, with diazotized aromaticamines.

6. The process for the production of a watersoluble azo dyestuff whichconsists in coupling an amine of the formula 01 N CH:

with diazotized 2,3,5,6-tetrachlor-l-aminobenzene. v

7. The process for the production of a watersoluble azo dyestufi whichconsists in coupling an amine of the formula with diazotized2,4,5-trich1or-l-aminobenzene.

8. The process for the production of a watersoluble azo dyestufi whichconsists in coupling an amine of the formula 01 N CH3 CHPCHrN-CH:

with diazotized 1-amino-2,6-dichlor-l-nitrobenzene.

9. Azo dyestuffs corresponding to the general formula,

wherein R1 and R stand for aryl radicles and at least one X stands foran 'alkyl radicle to which is attached in direct combination with analkyl carbon atom a quaternary nitrogen atom, the other X being a'memberof the group consisting of alkyl, cycloalkyl, aralkyl and aryl,

' 10. Azo dyestufis of the general formula C'H:C..HzNCH:

wherein R1 and R stand for aryl radicles and X stands for an alkylgroup.

11. Azo dyestufis of the general formula wherein R1 and R stand for arylradicles.

12. Azo dyestuff corresponding to the formula 01 o H 4 o 01 g C l/ VCHzCHzN-CHs o1 CH3 14. Azodyestuff corresponding to the formula HANSKRZIKALLA.

HEINRICH DEHNERT. DIETER VOSSEN.

